Quaternary thenyl phosphonium salts

ABSTRACT

1. A 2-THENYL-PHOSPHONIUM SALT OF THE FORMULA   2-R1-THIOPEN-5-YL-CH2-P(+)(-R3) X(-)   IN WHICH R1 IS HALO, R EACH INDIVIDUALLY IS BUTYL, AND X IS A MONOVALENT ANION SELECTEED FROM THE GROUP CONSISTING OF HALIDE, THIOCYANATE, NITRATE, O,O-DIETHYLDITHIOPHOSPHATE, O-ETHYL XANTHATE AND N,N-DIMETHYL DITHIOCARBAMATE.

United States Patent cc 47,947 r Patented Nov. 12, 1974 and 3,847,947 69 e QUATERNARY THENYL PHOSPHONIUM SALTS R"-CH;PR3.X

Peter F. Epstein, Prairie Village, Kans., assignor to l Chemagro Corporation r No Drawing. Continuation of abandoned application Ser. 0 s (Iii) No. 18,745, Mar. 11, 1970. This application July 3, in which 1972, Ser. No. 268,321

Int. Cl. C07d 63/14 R, R and R each individually is hydrogen, halogen or US. Cl. 260-4325 7 Claims alkyl of 1-4 carbon atoms,

ABSTRACT OF THE DISCLOSURE Quaternary thenyl phosphonium salts, i.e. [(optionally 2,3,4 and/or alkyl-substituted)-2- or 3-thenyl]-[tri(sarne or mixed) alkyl and/or aryl]-phosphonium salts, i.e. halides, cyanides, thiocyanates, 0,0-diethyl-dithiophosphates, nitrates, O-ethyl-xanthates and N methyl dithiocarbamates, which possess plant-growth regulating properties, including synergistic properties, and which may be produced by conventional methods.

This is a continuation of application Serial No. 18,745, filed Mar. 11, 1970, now abandoned.

The present invention relates to and has for its objects the provision for particular new quaternary thenyl phosphonium salts, i.e. [(optionally 2,3,4 and/ or 5-mono-di and tri [same or mixed] halo and/or aryl-substituted)-2- or 3-thenyl]-[tri (same or mixed alkyl and/ or aryl]-phosphonium salts, i.e. halides, cyanides, thiocyanates, 0,0-diethyl-dithiophosphates, nitrates, O-ethyl xanthates and N- methyl-dithiocarbamates, which possess valuable plantgrowth regulating properties, including synergistic properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way, especially for regulating, e.g. selectively retarding and/or promoting, the growth of plants or vegetation of the most varied kinds, including synergistic plant growth regulation, with other and further objects of the invention becoming apparent from a study of the within specification and accompanying examples.

It is known in the prior art that quaternary phosphonium salts, such as the quaternary phosphonium salt, (2,4-dichlorobenzyl)-(tri-n-butyl)phosphonium chloride, of the formula R each individually is an alkyl and/or optionally substituted aryl radical, and

X is a monovalent anion such as halogen, pseudo-halogen, and other monovalent anions,

exhibit strong growth-controlling, in particular growthinhibiting, effects without significant concomitant phytotoxic efiects.

It has furthermore been found, in accordance with the present invention, that the compounds of formulae (Ii) and (Iii) above may be produced by a process which comprises reacting a corresponding thenyl halide of the formula R, R" and R are the same as defined above, and Y is halogen with a tertiary phosphine of the formula PR (III) in which R is the same as defined above,

optionally in the presence of a solvent.

The nature of the anionic portion of the resulting molecule of the specific halide compound of formula (Ii) or (Iii) above so produced, i.e. X as defined above, can be varied, for example, by further reacting such specific halide compound of formula (Ii) or (Iii) with the alkali metal (e.g. sodium, potassium, and the like) or silver salt (IV) of the desired anion, or in other conventional ways which are readily apparent to anyone skilled in the art.

Surprisingly, the compounds of formulae (Ii) and (Iii) above according to the present invention show a more pronounced growth regulatory activity, with concomitantly reduced phytotoxicity, than the analogous quaternary phosphonium compounds known from the prior art, such as compound (A) noted above, which are chemically the closest active compounds having the same type of activity. The instant compounds, unlike said analogous phosphonium salts of the prior art, can be used significantly in the form of foliar sprays without appreciable phytotoxicity or destruction of chlorophyll when used at biologically efficacious rates. Additionally, unlike such analogous compounds of the prior art, the instant active compounds enhance synergistically the known biological efficacy of, for instance, compounds (B) and (C), i.e. S,S,S-tributyl phosphorotrithioate (DEF) and maleic hydrazide (MH-30) while, in the case of the latter, reducing the undesirable phytotoxicity associated with the use thereof alone at comparable rates. The active compounds according to the present invention therefore represent a valuable contribution to the art.

If, for instance, 5-chloro-2-thenyl chloride (IIia) and tri-n-butyl phosphine (HIa) are used as starting materials, the course of the reaction can be represented by the following reaction scheme:

(Ilia) IE) W 9 Cl S CH2P -(34 03 G1 The course of the anion exchange reaction in which (5- chloro 2 thenyl)-(tri-n-butyl)-phosphonium chloride 1) and potassium thiocyanate are used as starting materials can be represented by the following equation:

H o 9 Cli s GHgP (rt-BU) a. S CN(+K Cl) Advantageously, in accordance with the present invention, in the various formulae herein:

R, R" and R'" each individually represents hydrogen;

halo such as chloro, bromo, iodo and/or fluoro,

especially chloro and/or bromo; and/or straight and branched chain lower alkyl hydrocarbon of l-4 carbon atoms such as methyl, ethyl, nand iso-propyl, n-, iso-, sec.- and tert.-butyl, and the like,

such that R, R" and R" are the same or different groups;

R each individually represents straight and branched chain alkyl hydrocarbon of 1l2 carbon atoms such as methyl to terL-butyl inclusive as defined above, pentyl, hexyl, heptyl, In and iso-octyl, nonyl, decyl, undecyl, dodecyl, and the like, especially lower alkyl, C or C alkyl, and C or C alkyl and more especially n-butyl (i.e. n-Bu), iso-butyl, n-octyl and iso-octyl; phenyl; and/or lower alkyl-substituted phenyl such as 2-, 3- or 4- methyl to tert.-buty1 inclusive as defined above, -substituted phenyl, and the like, especially C or C or C alkyl-phenyl, and more especially 2-, 3- or 4-methyl-phenyl; such that the three R groups are the same or different;

and

X represents a monovalent anion including halide ion such as chloride, bromide, iodide and fluoride, especially chloride and bromide ions,

pseudohalide ion such as cyanide, thiocyanate, and

the like, especially thiocyanate ion,

0,0-diethyl-dithiophosphate ion, i.e. 0,0-diethyltbionophosphoryl-thiolate;

nitrate ion;

O-ethyl-xanthate ion; or

N,N-dimethyl dithiocarbamate ion.

It will be noted that the point of attachment of the phosphorus bearing side chain to the thiophene ring can 'be either in the 2- or 3-position of the nucleus depending on the intermediate used and on the nature of the substituents R, R" and R'.

Preferred compounds of the present invention include: (1 S-chloro-Z-thenyl) -(tri-n-butyl) -phosphonium chloride (3) 2-(thenyl)-(tri-n-butyl)-phosphonium chloride (4) -(2,5-dichloro-3-thenyl) (tri-n-butyl) -phosphonium chloride (5 (S-bromo-Z-thenyl) (tri-n-butyl) -phosphonium chloride (6) (2,5-dibromo-3-thenyl) (tri-n-butyD-phosphonium chloride (22 Z-thenyl) (tri-n-butyl) -phosphonium nitrate (23 (2,5 -dichloro-3-thenyl) (tri-n-butyl) -phosphonium nitrate 12) (5-br0mo-2-thenyl) (tri-phenyl) -phosphonium chloride 16) (2,5 -dichloro-3-thenyl)- tri-phenyl) -phosphonium chloride 18) (2,5 -dibromo-3 -thenyl) (tri-phenyl -phosphonium chloride l7) (S-chloro-Z-thenyl) (tri-phenyl) -phosphonium chloride (2) (5chloro-2-thenyl)- (tri-n-butyl)-phosphonium thiocyanate (24) (Z-thenyl -(tri-n-butyl) -phosphonium thiocyanate (25) 2,5 -dichloro-3 -t henyl) (tri-n-butyl) -phosphonium thiocyanate (9) (S-bromo-Z-thenyl) (tri-n-butyl) -phosphonium 0,0-

diethyl-dithiophosphate (26) (2-thenyl)- (tri-n-butyl) -phosphonium-0,0-diethylxanthate (27) (2,5-dichloro-3-thenyl (tri-n-butyl) -phosphonium- N ,N-dimethyldithiocarbamate (10) (5-chloro-2-thenyl) (tri-n-octyl)-phosphonium chloride (1 1 (5-bromo-2-thenyl) (tri-n-octyl) -ph0sphonium chloride l4) (S-bromo-Z-thenyl) -(tri-n-octyl phosphonium thiocyanate 19) (2-thenyl) -(tri-phenyl) -phosphonium chloride (20) (2-theuyl)- (tri-n-octyl) -phosphonium chloride (21) (S-chloro-2-thenyl) -(tri-n-octyl) -phosphonium thiocyanate (7 (Z-chloro-S-bromo-3-thenyl -(tri-n-butyl) -ph0sphonium chloride l3 3-thenyl) (tri-n-butyl) -phosphonium bromide l5 (S-chloro-Z-thenyl) -(dimethyl) (phenyl) phosphonium chloride In accordance with one embodiment of the present invention, R, R" and R' each individually is hydrogen; or one or more is either chloro or bromo; R is n-butyl; and X is a chloride, bromide, thiocyanate or nitrate ion; and more specifically in formula ('Ii) above, R is chloro or bromo; R" and =R' are both hydrogen; R is n-butyl; and X is a chloride, nitrate or thiocyanate ion, whereas in formula (Iii) above, R and R are both chloro or bromo; R" is hydrogen; R is n-butyl; and X is a chloride, thiocyanate or nitrate ion.

Preferably, R, R" and R'" each individually is hydrogen; or halo, especially chloro or bromo; R each individually is C alkyl, especially C or C or C or C alkyl; or phenyl; and X is a halide, especially chloride or bromide ion; or a thiocyanate ion or a nitrate ion; or an 0,0 diethyi-dithiophosphate ion, or an O ethyl xanthate ion, or an N,N-dimethyl dithiocarbamate ion.

More particularly, R and R'" each individually is hydrogen; or chloro; or bromo; R" is hydrogen; R is nbutyl; or n-octyl; or phenyl; and X is a chloride ion; or a bromide ion; or a thiocyanate ion; or a nitrate ion; or an 0,0-diethyl-dithiophosphate ion.

Most particularly, in formula (Ii) above, R is hydrogen; or chloro; or bromo; R" and R are both hydrogen; R is n-butyl; or phenyl; and X is a chloride ion, whereas in formula (Iii) above, R and R' are both chloro; or are both bromo; R" is hydrogen; R is n-butyl; or phenyl; and X is a chloride or a nitrate ion.

The types of starting thenyl halides usable in accordance with the process of the present invention are clearly characterized by formulae (Hi) and (111i) noted above.

These starting compounds are well known and can be prepared readily on an industrial scale. (See e.g. Henry D. Norris, US. Pat. 2,623,049.)

As examples of such starting thenyl halides which can be used in accordance with the present invention, there may be mentioned in particular:

2-thenyl chloride 3-thenyl bromide 5-chloro-2-thenyl chloride 5-bromo-2-thenyl chloride 5-methyl-2-thenyl chloride 2,5-dichloro-3-thenyl chloride 2,5-dibromo-3-thenyl chloride 2,4,5-trichloro-3-thenyl chloride 3,4,5-trichloro-2-thenyl chloride 2,4,5-tribromo-3-thenyl chloride 3,4,5-tribromo-2-thenyl chloride 2-chloro-5-bromo-3-thenyl chloride 2-bromo-5-chloro-3-thenyl chloride 5-iodo-2-thenyl chloride 5-fluoro-2-thenyl chloride 2-methyl-5-chloro-3-thenyl chloride 2,5-dimethyl-3-thenyl chloride, and the like.

The types of starting trialkyl, triaryl, or mixed tri-alkyl-aryl substituted phosphines usable in accordance with the process of the present invention are clearly characterized by formula (III) noted above.

These starting compounds are also well known and can be prepared readily on an industrial scale.

As examples of such starting trialkyl, triaryl, or mixed tri-alkyl-aryl phosphines which can be used in accordance with the present invention, there may be mentioned in particular:

tri-n-butyl phosphine tri-n-octyl phosphine triphenyl phosphine phenyl-dimethyl-phosphine, and the like.

The production reaction is carried out preferably in the presence of a solvent (this term includes a mere diluent), particularly one in which the solubility of the final product is not very high and which is inert to the reaction. Examples of such solvents include inert organic solvents, for example, hydrocarbons such as n-hexane, n-heptane, benzine, benzene and toluene; ethers such as diethyl ether, dioxane and tetrahydrofuran; lower boiling aliphatic nitriles such as acetonitrile; amides such as dimethyl formamide; alkyl sulfoxides such as dimethyl sulfoxide; aliphatic ketones such as acetone; chlorinated aliphatic hydrocarbons such as chloroform and dichloromethane; and the like; aliphatic alcohol esters of aliphatic carboxylic acids such as ethyl acetate and the like; and any desired mixtures of these solvents.

The use of anhydrous and non-hydroxylic solvents and the absence of oxygen are desirable factors in the optimization of yield and product quality but are not essential to the success of the reaction.

The reaction temperature can be varied within a fairly wide range. In general the reaction is carried out at substantially between about 20 C. and +130 C., preferably between about 20 C. and 80 C.

In general, for economy and efficiency, the reactants are used in approximately equimolar proportions. The reaction can, for example, be carried out in such a manner that the thenyl halide, for example S-chloro-Z-thenyl chloride, is added to a solution of the phosphine, for example trin-butyl phosphine, in anhydrous ether at room tem perature, and the reaction mixture allowed to stand for several days at room temperature, the resulting solid crystalline product being recovered by filtration. The product thus prepared can be obtained in a substantially pure form by repeated washings with cold anhydrous ether.

The 2- (or 3-) thenyl trialkyl, triaryl, or mixed trialkyl-aryl phosphonium halides thus prepared can, if desired, be converted correspondingly into other anionic phosphonium salts of the desired anionic component in the conventional manner in a solvent such as acetone, ethanol or dimethyl formamide in which both of the reagents are appreciably soluble. After separation of the metal halide (e.g. sodium, potassium, silver, and the like, halide) formed in the reaction, removal of the solvent under reduced pressure yields the desired salt in substantially pure form.

Advantageously, the active compounds according to the present invention exhibit strong growth-regulatory properties. Such compounds can therefore be used to 'alfect the rate of growth of plants. Since at rates and in concentrations showing high growth regulatory activity the instant active compounds have little or no phytotoxic action, these effects on plant growth can be obtained with little or no damage to useful plants. The instant compounds also possess comparatively low mammalian toxicity.

By plants are meant in the broadest sense all useful vegetation including valuable agricultural, horticultural, fruiticultural, and the like, crop vegetation, weeds, etc., the growth regulation of which is desired.

Thus, the active compounds according to the present invention can be used for stunting or retarding the growth of monocotolydenous and dicotolydenous crop and weed plants, ornamental plants, shrubs, and trees;

for increasing beneficially the yield, oil yield and protein yield of leguminous plants such as soybeans, lima beans, snap beans, peas, and the like;

for affecting the fruit set of spermatophytic plants, i.e. apples, peaches and other fruit of fruitbearing trees, shrubs or crop plants;

for increasing the resistance of vegetation, particularly fruit trees, to the damage caused by frost and drought;

for increasing the sugar content or yield of plants such as sugar beet, sugar cane, and the like;

for enhancing synergistically the defoliating action of S,S,S-tri-n-butyl phosphoro-trithioate (DEF) by increasing the percentage defoliation and by partially inhibiting the regrowth of foliage in defoliated plants, plarticularly cotton, soybeans and other similar types of p ants;

for retarding the growth of grasses such as Kentucky Bluegrass, fescue, and the like, by reducing both the clipping weight per unit area and the plant height, and thus providing a means of chemical mowing;

for enhancing synergistically the action of maleic hydrazide (MH-30) in retarding the growth of grasses such as Kentucky Bluegrass, fescue, and the like, by reducing both the clipping weight per unit area and the plant height, thus also providing such chemical mowing;

for reducing synergistically the tendency of maleic hydrazide (MH30), when used alone at comparable rates, to produce phytotoxic injury to grass plants such as Kentucky Bluegrass, fescue, and the like;

for inhibiting or partially inhibiting the undesirable growth of suckers on plants, particularly tobacco plants;

for enhancing synergistically the effect of maleic hydrazide (MH30) for the aforesaid use of inhibiting undesirable growth of suckers on plants, without infiicting appreciable phytotoxic damage or otherwise affecting adversely the quality of the crop;

for affecting, i.e. breaking the dormancy of plants, such as potato plants and the like, by causing them to sprout.

As aforesaid, significantly, the instant active compounds can be used in the form of foliar sprays without appreciable phytotoxicity or destruction of chlorophyll, i.e. at the biologically efiicacious rates normally applied.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional, preferably inert (i.e. plant compatible or herbicially inert), pesticide diluents or extenders, i.e. diluents or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compound with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers, optionally with the use of carrier vehicle assistants, e.g., conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents whereby, for example, in the case where Water is used as diluent, or ganic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for the purpose: inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), parafiins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. dichloromethane, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. Z-aminoethanol, etc.), ethers, ether-alcohols (e.g. Z-methoxyethanol, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.) and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolin, alumina, silica, chalk, i.e., calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/ or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as conventional plantgrowth regulators, fungicides, insecticides, nematicides, bactericides, selective herbicides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions,

suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95%, and preferably 0.5- 90%, by weight of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 001-5 .0%, preferably 0.010.8%, by weight of the mixture. Thus, the present invention contemplates overall compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vhicle assistan, e.g., surface active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.01%, and preferably 0.01-5.0%, by weight of the mixture.

Conveniently, the instant active compounds, having appreciable solubility in Water, are preferably usable in the form of aqueous solutions containing substantially between 0.01% and 5%, preferably 0.01%-0.8%, by weight of the active compound, with or without the addition of stabilizers, surface active agents, etc., as mentioned above. Such solutions are particularly useful for direct foliar spray application, in which as noted above (unlike the analogous quaternary phosphonium compounds of the prior art) they do not cause appreciable phytotoxic plant injury at efficacious growth regulating rates of application.

The active compounds can also be used in accordance with the well known ultradow-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50l00 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufiicient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by wegiht of the active compound or even the active substance alone, e.g. about 20100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively controlling the rate of growth of plants; e.g. stunting plant growth, increasing plant or fruit yield, protein yield, oil yield, sugar yield, resisatnce to frost and drought damage; synergising defoliating action and inhibiting regrowth; eifecting chemical mowing; preventing the growth of undesirable suckers; breaking plant dormancy and the like; which comprise applying to at least one of (a) such plants and (b) their habitat, i.e. the locus to be protected or controlled, an efficacious or growth rate controlling amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for example, by spraying, atomizing, scattering, dusting, watering, sprinkling and the like, either to the soil around the plants, the plants themselves, or both.

It will be realized, of course, that in connection with the use of the instant compounds for influencing the growth of plants and/or effecting the other desirable results heretofore mentioned, the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application and may be varied within a fairly wide range depending upon the weather conditions, the purpose for which the active compound is used, e.g. growth promoting or growth retarding effect, and the plant species in which it is intended to produce the desired effect. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The outstanding growth regulatory activity of the particular active compounds of the present invention is illustrated, without limitation, by the following examples.

EXAMPLE 1 pylene oxide and propylene glycol (mol. wt. about 1000) (Pluronic L-61) To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed intimately with 1 part by Weight of the stated wettable powder base, and the resulting mixture is diluted with water to the desired final concentration. A piece of round filter paper (150 mm. diameter) is placed in a 150 mm. x 25 mm. Petri dish, and 10 cucumber seeds are arranged in a row on the paper. The filter paper is then moistened with 7 mls. of the preparation of the given active compound.

The so-treated dish is incubated in darkness at 22 C. Rating is determined on the basis of growth response of the root during the period of twenty-four (24) hours between the third and fourth day of incubation.

A to 9 scale rating is used to indicate the activity of potential growth retardants. A 0 scale reading indicates growth retardation with the range of 010% as compared with the control. A 9 scale reading corresponds to 90% or more growth retardation. On the other hand, figures in parentheses indicate growth promotion or enhancement. Thus, a (0) to (9) scale rating is used to indicate the activity of potential growth promotants. (0) indicates growth promotion within the range of 0-10% as compared with the control, whereas (9) indicates 90% or greater growth promotion when compared with the control.

The particular active compounds tested, the amounts used and the results obtained can be seen from the following Table 1.

TABLE 1 Concentration Active compound 10,000 1,000 100 Cl CH 63 B 31 \S/ 2P(Tl.- 11):-

(31) Same as above 9 9 9 69 6 Br- S CH2P(nBu)a-Cl 9 6 Br- 8 CHzPPha-Cl CHeP (n-Buh-Cl CHzPPha-Cl Cl- 01 S 1 CHzP(!L-B11)a-Cl Br- Br S CH PPhrCl Br- Br S C1 CH I H e S 2 -Ca i1)a-Cl 63 9 BI-\s CH2P(7Z-C8H11)!'C1 TABLE 1Continued Concentration Active compound 10, 000 1,000

93 9 01- s CHzP('n-Bt1)3- S ON G3 9 01- s CHzP (n-CaHnh S ON 69 9 Br- S CHzP(1L-CBH17)3 SCN 69 6 II Brs CHzP(n-Bu)aSP(OEt)z Q e S 2 s 11)aCl H CH i Pl e S 2 13- C1 [I s 6 S CHzPQ/l-BlDa-NO! lH-CH P (n-BuhN a 01 8 -Cl H a e S CHzP(n-Bu)a-SCN ITFCH: P(n-Bu)a-SCN 9 Ol- S Cl H CH B e i s 2 (72- IJ)3'S- OCZH5 I H-CH2P (n-Bu)a- S iN(CH C1 s Cl EXAMPLE 2 Snap Bean Foliar Spray Test Wettable powder base consisting of:

92 parts by weight hydrated silica (ultra fine, Hi-Sil 4 pars by weight sodium lignin sulfonate (Marasperse 4 parts by Weight polycondensate of ethylene oxide, propylene oxide and propylene glycol (mol. wt. about 1000) (Pluronic L-61) To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed intimately with 1 part by weight of the stated wettable powder base, and the resulting mixture is diluted with water, containing 0.01% polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier, to the desired final concentration.

Snap bean plants, as soon as the primary leaves are relatively smooth (6-7 days old) and are capable or absorbing and translocating chemicals, are sprayed (treated) with the given active compound preparation at the indicated concentration until just dew moist. For each test pared with the control, whereas (9) indicates 90% or greater growth promotion as compared with the control.

The particular active compounds tested, the amounts used and the results obtained can be seen from the following Table 2.

TABLE 2 Concentration (p.p. m.)

Active compound a b c a b e b c (A) 31 (a m 1 4 o o G 9 Cl- CH2P (n-Bu) o! (known) Cl C e S H: (n-Buh-Cl G9 9 CH1P(n-Bu)s-Cl S (52)..-.:.:.';-: t) l) t) t) v) 2 2 0 o e Br s H2 (n-BlDz-Cl GB 9 B1 .S --CHg?Ph:-Cl

4 v Q 6 a e o e a n o o a 2 M DT J U (J Cll- S -Cl 0 1B 2: 9 9 1 3 2 0 0 0 O 0 2) CHaPPha-Cl C1- s C1 C a e C1 s H2 Pha-Cl 6 ....'..::::r. 69 9 0 O (2) CHEPGWBQS'CI U O Br S -Br 18 "222: G3 9 0 0 0 O 0 O O 0 2) onirrm-ol 0 Br S -Br N0'rn.In this table, the letters a, b and 0 refer respectively to total plant height, length of second node to apex, and petiole length of the first trifoliate leaves.

*Indicates plants died due to phytotoxicity.

4O mls. of the appropriate compound dilution are sprayed on 4 plants in an area of five square feet.

The so-treated plants are moved to a greenhouse and remain there for 10 to 14 days. The degree of growth re sponse is determined by measuring three parameters: total plant height, length of second node to apex, and petiole length of the first trifoliate leaves.

A 0 to 9 scale reading is used to express the degree of potential growth retardation. A 0 scale reading indicates growth retardation within the range of 0% to 10% as compared with the control. A 9 scale reading corresponds to 90% or more growth retardation.

A (0) to (9) scale rating is used to indicate the activity of potential growth promotants. (0) indicates EXAMPLE 3 Snap Bean Yield Test Solvent: 9.5 ml. of water containing 0.01% by weight of polyoxyethylene soribtan monolaurate (Tween 20) as emulsifier.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rate of application indicated below in p.p.m.

Snap bean plants, when 5% to 10% of the flowers are growth promotion within the range of 0-10% as com- 7 in bloom, are sprayed (treated) with the given active compound preparation at a rate of 92.625 decaliters per hectare. The control plots receive no such treatment.

At harvest time the fresh weight of fruit from the treated and untreated plots is determined. The increase in yield of the treated plots is expressed as a percentage of the control yield.

The particular active compound tested, the rate of application and the results obtained can be seen from the following Table 3.

height of 2.45 cm. from the ground to determine the foliage yield from each plot;

(b) Grass growth by visual ratings that are based on a to 100 scale, where 0 indicates no reduction in growth when compared with the control plots and 100 indicates complete suppression of additional grass growth.

The particular active compound tested, the rates of application and the results obtained can be seen from the following Table 4.

TABLE 4.CHEMIOAL MOWING OF KENTUCKY BLUEGRASS P.p.m. of P.p.m. of Average fresh active maleic green weight compound hydrazide of the Visual Active compound applied applied clippings, g. rating EXAMPLE 5 TABLE 3.SNAP BEAN YIELD TEST Chemical Mowing of Kentucky Bluegrass Solvent: 9.5 ml. of water containing 0.01% by weight of polyoxyethylene sorbitan monolaurate (Tween as emulsifier.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in ppm.

The preparation of the mixture of the particular active compound with maleic hydrazide (MH-) is made by mixing together one part by weight of the given active compound and 3 parts by weight of maleic hydrazide (MH-30), mixing 0.5 g. of the resulting mass with the stated amount of solvent containing the stated amount of emulsifier, and then further diluting the concentrate so produced with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

Growing bluegrass sod is sprayed with the particular active compound preparation at the concentrations indicated. The treatment test plots are arranged in a randomized block design with 3 replications. The plots are mowed to a uniform height of 5 centimeters before spraying and then left for 5 weeks before readings are taken.

The degree of efiicacy of the particular active compound is evaluated by two methods:

(a) A clipping from a 30 cm. x 30 cm. area at a Chemical Mowing of Kentucky Fescue Solvent: 9.5 ml. of water containing 0.01% by weight of polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

The preparation of the mixture of the particular active compound with maleic hydrazide (MH-30) is made by mixing together one part by weight of the given active compound and 3 parts by weight of maleic hydrazide (MH-30), mixing 0.5 g. of the resulting mass with the stated amount of solvent containing the stated amount of emulsifier, and then further diluting the concentrate so produced with such solvent containing said emulsifier to provide the rates of application indicated below in ppm.

Growing fescue grass sod is sprayed with the particular active compound preparation at the concentrations indicated. The treatment plots are arranged in a randomized block design with 3 replications. The plots are mowed to a uniform height of 5 centimeters before spraying and then left for 8 weeks before readings are taken.

The degree of efiicacy of the particular active compound is evaluated by two methods:

(a) A clipping from a 30 cm. x 30 cm. area at a height of 2.45 cm. from the ground to determine the foliage yield from each plot;

(b) Grass growth by visual ratings that are based on a 0 to scale, where 0 indicated no reduction in growth when compared with the control plots and 100 indicates complete suppression of additional grass growth.

The particular active compound tested, the rates of application and the results obtained can be seen from the following Table 5.

TABLE 5.CHEMICAL MOWING OF KENTUCKY BLUEGRASS P.p.m. of P.p.m. of Average fresh active maleic green weight compound hydrazide of the Visual Active compound applied applied clippings, g. rating ll H B C S C 3 (nu);- 01

Same as above 1, 250 3, 750 64. 3 15 0 0 5000 79.2 7 Control 0 0 103. 2 0

15 16 EXAMPLE 6 emulsifier to provide the rates of application indicated below in ppm. Chemical P nin of Elm Trees Soybean plants of the variety Clark 63 are used as test plants, and are sprayed (treated) with the given active Solvent: 9.5 ml. of water containing 0.01% by weight compound preparation at a rate of 92.625 decalitres per of polyoxyethylene sorbitan monolaurate (Tween 20) as hectare, at a time when less than of the flowers are emulsifier. in bloom. The treatment plots are arranged in a random- To produce a suitable preparation of the particular acized block design with three replications. The control tive compound, 0.5 g. of such active compound is mixed plots receive no such treatment. with the stated amount of solvent containing the stated The degree of eflicacy of the given active compound is amount of emulsifier, and the resulting solution is then determined by weighing the seeds harvested from the given further diluted with such solvent containing said emulsiplot, Th percentage r du tion of plant height i the fier to provide the rates of application indicated below in treated plots, when compared with the untreated control p.p.m. plots, is also included in the evaluation.

The preparation of the mixture of the particular active The particular active compound tested, the rates of apcompound with maleic hydrazide (MH-30) is made by plication and the results obtained can be seen from the mixing together one part by weight of the given active f ll in T bl 7,

TABLE 7.SOYBEAN YIELD TEST P.p.m. of Percent Average active increase of plant compound soybean height Active compound applied yield (0111.)

, l i Q 9 S CH,P(n-Bu) -C1 Same as above C ontrol g 5 13?: 3

compound and 3 parts by weight of maleic hydrazide EXAMPLE 8 (Mil-), mixing 0.5 g. of the resulting mass with the stated amount of solvent containing the stated amount of p i l Test emulsifier, and then further diluting the concentrate so produced with such solvent containing said emulsifier to Solvent: 95 m1 of Water containing by weight provide the rates of application indicated below in ppm. o 01 3-year-old American Elm trees are used as test plants. g gf Sorbltan monolaurate (Tween 20) as The treatments are applied by spraying the given prepa- To produce a suitable re aration of the articular ratloh. 0n 2 11131175 P f 'Wlth rephcauons' T active compound, 0.5 g. of s ilcli active compound is mixed ial'datloh of twlgg growth determmfid by measurmg i 40 with the stated amount of solvent containing the stated length of the twlg 17 weeks after i and q? amount of emulsifier, and the resulting solution is then It to the length of the Same twlg be ore treatment e further diluted with such solvent containing said emulrcentage owth of the twi is compared with the pergg i of Inmate; twigs and the result slfier to provide the rate of application indicated below pressed as percent inhibition of growth of the treated twigs Pea plants, when 5% to 10% of the flowers are in The particular active compound tested, the rates of apbloom, are ay (treated) with the given active plication and the results obtained can be seen from the Pound preparation at a rate of 92.625 decaliters per hecfollowing Table 6. tare. The treatment plots are arranged in a randomized TABLE 6.GHEMICAL PRUNING 0F ELM TREES P. r P. t P

505%" W initiitfitl ti compound hydrazide growth of Active compound applied applied treated twig Oil OH 901 Bu) %l Same as above 200 0 26 d0 40 7 ....do 1,250 3,750 42 .-...do 750 25 ..do.. 0 5, 000 31 do 0 1,000 39 do- 0 500 40 Control. 0 0

EXAMPLE 7 block design with 3 replications. The control plots receive Soybean Yield Test no such treatment.

At harvest time the fresh weight of fruit from the Solvent: 9.5 ml. of water containing 0.01% by weight treated and untreated plots 1s determined. The increase in of polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier. yield of the treated plots is expressed as a percentage of To produce a suitable preparation of the particular the comm1yie1 active compound of Such active compound is The particular active compound tested, the rate of apmixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is Phcatlon and the results Obtamed can be Seen from the n turther diluted with such solvent containing said following Table 8.

TABLE 8.-PEA YIELD Apple Fruit-Set Test lSolvent: 9.5 ml. of water containing 0.01% by weight further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in ppm.

Ten-year-old Redhaven peach trees are used as test plants, and single limbs of these trees are sprayed (treated) with the given active compound preparation at a rate of I 277.785 decaliters per hectare 5 days after full bloom. Each treatment is" replicated 3 times and each replicate is on separate trees. The control plots receive no such treatment.

The degree of eflicacy of the given active compound is determined by subtracting the number of fruits remaining on the treated limbs at hand thinning time from the original number of flowers set per limb that are counted prior to treatment.

The particular active compound tested, the rates of application and the results obtained can be seen from the following Table 10.

HTABLE 10.-PEACH FRUIT-SET TEST P.p.m. of active compound Percent increase Active compound applied in fruit set (112) l 60 7 l I w 01 m OH? e 2 (TL-BlDg-Cl 3...... as above l 43 Control 0 0 of polyoxyethylene sorbitan monolaurate (Tween as EXAMPLE 11 emulsifier.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in ppm. v v t v Six-year-old Golden Delicious apple trees are used as test plants, and single limbs of these trees aresprayed (treated) with the given active compound preparation at a rate of 277.785 decaliters per hectare twelve days after full bloom. Each treatment is replicated 3 times and each replicate is on separate trees. The control plots receive no such treatment.

The degree of efiicacy of the given active compound is determined by substracting the number of fruits remaining on the treated limbs after June drop from the'original' number of fruit set per limb that are counted prior to treatment. I

The particular active compound tested, the rates of application and the results obtained can be seen frorn the following Table 9.

TABLE 9.-APPLE FRUIT-SET TEST P.p.m. of Percent active increase compound in fruit Active compound applied set EXAMPLE 10 Peach Fruit-Set Test Defoliant-Desiccant-Regrowth Control Test (Synergism with S,S,S-tri-n-butyl phosphorotrithioate-DEF.

Solvent: 24.5 ml. water containing 0.01% by weight of polyoxyethylene sorbitan monolaurate (Tween 20) as To produce a suitable preparation of the particular active compound, 0.5 gram of such active compoundis 7 active compound with S,S,S tri-n-butyl phosphorotrithioate v (D EF), the two ingredients are mixed in the proportions of 1 part by weight of such given active compound with respectively 1, 2 and 4 parts by weight of said S,S,S-tri-nbutyl phosphorotrithioate (DEF); then 0.5 g. of each of 1 these mixtures is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containingsaid emulsifier to provide the rates of application indicated below in kg. of active ingredient per hectare, in a total volume of 32 decaliters per hectare.

Cotton plants in the squaring (pre-bloom) stage are sprayed with the given active compound preparation until just dew'moist. For each test, 25 mls. of the appropriate active compound or synergistic mixture dilution are sprayed on two plants in an area of five square feet. The number of leaves on the plants is recorded.

After 7 days, the degree of desiccation is determined and expressed as a percentage, wherein 0% means that there is no desiccation and 100% means that there is complete desiccation.

After 7 days, the degree of defoliation is also determined and expresed as the percentage of the leaves which I defoliated, i.e. which fall from the particular plant, wherej' in 0% means that there is no defoliation and 100% means that there is'complete defoliation.

After 7 days, the degree of regrowth inhibition is also "determined and expressed as a percentage, wherein 0% means that there is no regrowth inhibition and means that there is complete regrowth inhibition.

The particular active compound and synergistic mix- '19 20 tures tested, the rates of application, and the results obrelatively smooth (6-7 days old) and are capable of abtained can be seen from the following Table 11. sorbing and translocating chemicals, are sprayed (treated) TABLE 11.-DEFOLIANT-DESICCANT-RE GROWTH CONTROL TEST Rate of Rate of first second active active compound compound applied, applied, Defolietion at- Regrowth kg./ Second active (kg. control b First active compound hectare compound hectare 5 days 7 days at 7 days (in) 1. 12 t) 1. 12 124 100 so i I (B B C] (B) (n-Bu)=SPS-n-Bn Cl GHrP (n u):

(known) I Defoliation data is based on percent of S,S,S-tri-n-butyl phosphorotrlthioate (B) (DEF) where 100 is equal to trithioate (DEF) alone at the same rate, Le. 1.12 or 0.6 kgJhect-are as the case may be. 7,

b Rating: 0 is no effect; 100 is complete inhibition of new growth.

Figures in parentheses is actual percent defoliation from treatments with S,S,S tri-n-butyl phosphorotrithioate (DEF) a corresponding stated rate.

EXAMPLE 12 p with the given active compound preparation at the indicated concentration until just dew moist. For each test,

40 mls. of the appropriate compound dilution are sprayed on 4 plants in an area of five square feet.

Comparative (Ihlorophyll Destruction Test (in foliar application) i t The so-treated plants are moved to a greenhouse and Wettable powder base conslstmg remain there for 10 to 14 days. The degree of growth 92 parts by weight hydrated silica (ultra fine, Hi-Sil response is determined by measuring two parameters: 23 3) total plant height, and the petiole length of the first tri- 4 parts by weight sodium lignin sulfonate .(Marasperse foliate leaves; and the percentage chlorophyll destruction N) -in the primary and trifoliate leaves is also measured.

4 parts by weight polycondensate of ethylene oxide, -.pro- The particular active compound tested, the rates of pylene oxide and propylene glycol (mol... wt. about application in p.p.m. and the results obtained can be seen 1000) (Pluronic L-61) 1 3 'from'the following Table 12.

TABLE 12l-COMPARAT1VE "onnonornvr r pgsrnuo'rron TEST (1N FOLIAR APPLICA- Petiole length 0! Percent chlorophyll P.p.m. of 1st destruction aetivg 'hlfltfit itrifoliatgm r. 1 compoun erg ea rimary 0 ate Active compound applied (0.111.) (cm.) leaves leaves C1. ..CH2g(%Bu)a-C1 ,(known) I 1;000 12.0 2.3 "70 0 I 100 21.2 9.6

(no e 10, 000 11. 4 0. 7 00 20 1,000 12.8 1.2 so 0 v B g 100 19.3 8.4 0

l. v 11)a- *Plants were lost due'to chemical injuries. of the primary leaves were abscissed and the remainder scored losses of chlorophyll content.

To produce a suitable preparation of the particular ac- Conclusion.-Foliar spray applications with active comtive compound, 1 part by weight of such active compound pound (1) resulted in somewhat reduced chlorophyll deis mixed intimately with 1 part by weightof the statcd struction when compared with the above-noted known Wettable powder base, and the resulting mixture is diprior art compound (A).

luted with water, containing 0.01%. polyoxyethylene sor- E-ven more significant is the fact that the latter, at a bitan monolaurate (Tween 20) as emulsifier, to the deratev of 10,000 p.p.m., was too phytotoxic to evaluate the sired final concentration. 7 75. chemical efiect thereof, while at a rate of 1,000 p.p.m.

Snap bean plants, as soon as the primary leaves are it induced 50% abscission of the primary leaves. By contrast, such active compound (1) showed no abscission of the primary leaves at any of the rates tested.

The process for producing the instant active compounds according to the present invention is illustrated without limitation by the following further examples:

EXAMPLE 13 C l EE 6 l s ,-CH; P (n- C4119) Cl 249 g. (1.5 M) of -chloro-2-thenyl chloride are dissolved in 1,000 ml. of anhydrous diethyl ether, and 303 g. (1.5 M) of tri-n-butyl phosphine are added over 1 hr. at ambient temperature with vigorous stirring.

A white precipitate begins to form after 20 minutes. The mixture is allowed to stand for 5 days and the precipitate removed by filtration, washed with anhydrous ether and air-dried.

386.5 g. (70% of the theory) of 5-chloro-2-thenyl-trin-butyl phosphonium chloride are obtained, mp. 157- 159 C.

The following compounds are prepared in analogous manner:

Compound N0.

Structure M.P., C.

H a e S CH2P(7L-B11)3'C1 69 6 Br- S -CH2P (n-Bu) C1 03 6 Br S CH2PPh3Cl CHzP(!Z-B11)3C1 Cl- 01 S CH P PhaCl Cl Cl S (B 9 01- s CH2PPh;Cl

OH P (n-Bu) Cl Br- IBr S (183) ED 9 (Waxy solid).

'CH2PPl13Cl Br- Br S H H 3F]: 31 S O z a (202) (Sticky solid).

l I H a H e S -C 2 (n-Ca 10301 L a 9 C1- 8 CH P (n-CsHi-l) 3G1 69 9 Br- S -CHzP (n-Cs 11)aCl 22 EXAMPLE 14 1.5 g. (0.05 M) of 5-chloro-2-thenyl tri-n-butyl phosphonium chloride, prepared according to Example 13, are dissolved in a mixture of ml. acetone and 10 ml. anhydrous ethanol. A solution of 4.9 g. (0.05 M) potassium thiocyanate in 60 ml. acetone is added with vigorous stirring.

The white KCl precipitate, which forms instantly, is allowed to age and then removed by filtration and discarded. The solvent is removed from the filtrate by stripping and the residue taken up in ethyl acetate, filtered remove any unreacted starting materials, and stripped again.

The resulting yellow oil, on trituration with hexane, yielded a solid.

18.6 g. (97% of the theory) of 5-chloro-2-thenyl-tri-nbutyl phosphonium thiocyanate are obtained, mp. 36 C.

The following compounds are prepared in analogous manner:

Compound number Structure M.P., C.

(212) Liquid, nn

1.5243. l l 6 Cl- CH2P(n-C3H17)3SCN (92) Liquid, m

S 1.5544. B CH 13 P OE r S 2P(n-v u)3- t):

(142) Liquid n 1.5282. B CH%( C 11 )S N l l B S -O 2P(nu)3-SCN All- C Hz]? (n-Bu) s- S C N 49-51 01 01 m CH? B G Et S 2 )s' O 65 9 II N CHzP(n-Bn)a'S-CNMe2 C1 01 EXAMPLE 15 10.0 g. (approx. 0.03 M) of Z-thenyl tri-n-butyl phosphonium chloride, prepared according to Example 13, is dissolved in 50 ml. boiling ethanol and added to a refluxing solution of 5.1 g. (0.03 M) of silver nitrate in 200 ml. ethanol; with vigorous stirring.

The white AgCl precipitate, which forms instantly, is allowed to age and then removed by filtration and discarded. The solvent is removed from the filtrate by stripping.

The resulting yellow oil, on trituration with ethyl acetate, yields a solid.

Compound number Structure It will be realized by the artisan that all of the foregoing compounds contemplated by the present invention possess one or more of the desired plant growth regulating properties, as well as a comparatively low phytotoxicity and a concomitantly low mammalian toxicity, enabling such compounds to be used with correspondingly favorable compatibility with Warm-blooded creatures for more effective growth-regulating, e.g. growth-promoting and growth-retarding, purposes.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention, which is to be limited only by the scope of the appended claims.

What is claimed is:

1. A Z-thenyl-phosphonium salt of the formula in which 1 l R S CH1? R .X

R is halo,

R each individually is butyl, and

X is a monovalent anion selected from the group consisting of halide, thiocyanate, nitrate, 0,0-diethyldithiophosphate, O-ethyl xanthate and N,N-dimethyl dithiocarbamate.

2. Compound according to claim 1 wherein R is selected from the group consisting of chloro and bromo, and X is a monovalent anion selected from the group consisting of chloride, bromide, thiocyanate, nitrate, 0,0- diethyl dithiophosphate, O-ethyl Xanthate and N,N-dimethyl dithiocarbamate.

M.P., O 0.

24 3. Compound according to claim 1 wherein said R is selected from the group consisting of chloro and bromo, and X is chloride.

4. Compound according to claim 1 wherein such compound is (5-chloro-2-thenyl)-(tri-n-butyl)-phosphonium chloride of the formula 5. Compound according to claim 1 wherein such compound is (S-bromo-Z-thenyl)-(tri-n-butyl)-phosphonium chloride of the formula 6. Compound according to claim 1 wherein such compound is 5-chloro-(2-thenyl)-(tri-n-butyl)-phosphonium thiocyanate of the formula 7. Compound according to claim 1 wherein such compound is (S-chloro-Z-thenyl)-(tri-nbutyl)-phosphonium chloride of the formula l H e e G] S CH2P(17.Bu)a.C1

References Cited UNITED STATES PATENTS 3,230,069 1/1966 Preston 712.7 3,268,323 8/1966 Goyette 71-23 OTHER REFERENCES Shevchuk, et al., Chem. Abs. 60, 15810-1 (1964). Jones, et al., Chem. Abs. 63, 12517 (1965).

JOHN D. RANDOLPH, Primary Examiner US. Cl. X.R.

W69) um i M b IA U'JI) 1. Al 1.51" 1' Ul' MCI) CERTIFICATE Oi CORRECTION Patent No. 3 7,9 7 Dated November 12 1974 Inventor(s) Peter F. Epstein (Page 1 of 2) and that said Letters Patent are Col. 0

Col.

Col.

Col.

It is certified that error appearsin the aboye-identified patent hereby corrected as shown below:

7, line 72, cancel "vhicle assistan" and substitute vehicle assistant 9, Table 1, .Compound (3 cancel "Same as abowe.

and substitute 6 v s -C11: (u-lluh-(Jl 14, in the heading of Table 5, cancel "BLUEGRASS" and substitute FESCUE 13, Table 5, Compound (1 correct formula to read as follows:

18, Table 10, under heading "P.p.m. of... ...applied" cancel and substitute 20 19, Table 11, Compound-(1 correct formula to read as follows 19, Table ll Compound (B), correct formula to read as follows:

Patent No. 3,847,947 Dated November 12, i974 Inventor(s) I (Page 2 of 2) Q It is certified that error appearsin the aboyc-identified patent and that said Letters Patent are hereby corrected as shown below:

Col l9 Table ll, in the footnote after "(DEF) cancel "a" and substitute at Col. 22, line 6, cancel "1.5 g" and substitute 18.5 g

. Col. 22, in Example 14 Table, Compound (26 correct the formula to read as follows Col. 22, in Example 14 Table, Compound (27 correct the formula to read as follows Col. 23, claim l, line 3 after the structural formula,

cancel "R each individually is butyl" and substitute R is butyl C01. 24, cancel claim 7.

L I Signed and Sealed this Q [SEAL] Twenty-first D f September 1976 Arrest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner nfParents and Trademarks 

1. A 2-THENYL-PHOSPHONIUM SALT OF THE FORMULA 